Coated fabric



Patented N... 18, 1947 UNITED STATES PATENT OFFICE COATED FABRIC David J. Sullivan, Falrfield, Conn., asslgnor to E. I. du Pont de N emours & Company, Wilmington, DcL, a corporation of Delaware No Drawing. Application April 27, 1945,

- Serial N0. 590,715

11 Claims. 1 This invention relates to an improved process for coating fabrics which are particularly adapted for upholstery purposes. I l

A great variety of coating compositions and systems have been employed in the manufacture of coated fabrics designed particularly for use as upholstery coverings in the construction of furniture, transportation vehicles including pleasure automobiles, trucks, busses, railway cars and the like where requirements with respect to appearance and general durability, Particularly wear resistance, are exceedingly severe. Compositions based on varnishes, cellulose derivatives, rubber and synthetic resinous materials have been used in finishing systems for the manufacture of upholstery but have been deficient in one or more of the essential requirements offlexibility, adhesion, tdughness, durability on outdoor exposure, resistance to staining and retention of elasticity on aging.

This invention has as an object the provision of a system for manufacturing upholstery which affords a finished product of markedly'superior properties. Another object is the provision of an upholstery finishing system in which the top coat is susceptible to controlled halogenation, thus affording a durable, case-hardened finish with improved surface slip. Another object is the provision of finishes, particularly adapted for the manufacture of upholstery, which are resistant to staining from oils, greases, cosmetics and foodstuffs. Another object is the provision 2 consisting of rubber, sulfur modified chloroprene (chloro 2 butadiene-l,3) acrylonitrile butadiene interpolymers (Hycar, Perbunan) and butadiene-styrene lnterpolymers (Buna S) and a top-coat containing a chloroprene (neoprene)- acrylonitrile lnterpolymer, preferably containing about 18 percent acrylonitrile, as essential ingredients, applied to a fabric substrate and subsequently halogenated.

The following examples are given by way of illustration only and no limitations are intended thereby except as indicated in the appended claims. V

Cotton duck sateen weighing about one pound per 54" yard was base coated by means of conventional spreader application with about two ounces per square yard of the following composition:

The accelerator-softener consisted of Latac (hexamethylene ammonium hexamei'hylene-dithlocarbamate).

of upholstery finishes which are remarkably wear.

resistant. Another object is the provision of upholstery finishes which are characterized by superior durability, when exposed outdoors and which are distinguished by outstanding resistance to heat, light, oxidation and cracking at low temperatures. Another object is the provision of a finish which affords better definition of grain when embossed and which retains the grain for longer periods of time. A further object is-the provision of finishes for fabrics which'are tough and flexible and which afford superior aging properties. A further object is the provision of finishes for fabrics which are highly adherent to the fabric substrate. A still furtherobject is the provision of finishes for fabrics which afford improved re'iistance to water and to abrasion. Other objects will become apparent as the description of the invention proceeds.-

These objects are accomplishedin accordanc with the present invention, by means of a plurality of coatings comprising at least one coating containing an elastomer selected from the group i The anti-ox dant consisted of N, p-tolyl N, p-tolyl sulionyl p-phenylene diamine manufactured and sold by Naugatuck Chemical Company as MUF. Other conventional anti-oxidants such as di-beta-naphthol para phenylene diamine can be substituted however for'the MUF with satisfactory results.

The neoprene used in this example was a. sulfur modified chloroprene containing about 0.75 percent of sulfur prepared in accordance with the procedures described in U. S. Patent 2,264,173, particularly Example 25.

The composition was prepared by the conventional process of combining the materials in a heavy duty kneading machine, such as a Banbury mixer after which it was dissolved in xylene (approximately 40 parts of composition to parts ofxylene) to spreader viscosity by mixing in an agitator mixer.

The fabric carrying the above described uncured base coat was then calender coated in an amount of about 9 ounces of the following composition which was prepared as in Example 1 by combining the materials in a heavy duty kneading'machine such as a Banbury mixer.

3 E'zzample 2 Percent by weight Neoprene 33.90 Accelerator-softener .06 Stearic acid .18 Crown clay 36.80 Anti-oxidant (MUF) .12 Chrome tanned ground leather 9.67 Red lake (azo pigment dyestuif) 1.94 Chrome yellow pigment 1.94 Red lake (precipitated azo pigment dyestuif 1.94

Circo" oil 2.91 Titanium-calcium pigment 4.84 Zinc oxide 1.45 Magnesium oxide 1.45 Dibutyl ammonium oleate 2.90

The neoprene, accelerator-softener and antioxidant used in this composition were of the same type as described in Example 1. The Circo oil is a petroleum process 011 of low aniline point.

Immediately following the application of the Example 2 coating, a top coat of the following composition thinned to spreader Viscosity in a proportion of about 40 parts by weight of the composition to 60 parts of a solvent consisting of nitropropane was applied in an amount of about /2 ounce per square yard by conventional knife coating process.

This composition was prepared by combining the materials on a rubber roller mill after which the homogeneous mixture was dissolved in nitropropane in the proportions previously indicated in a high speed agitator mixer.

The chloroprene-acrylonitrile interpolymer used in this example which contains about 18% acrylonitrile may be prepared in accordance with the procedure described in U. S. Patent 2,066,331 (Carothers et al.).

The coated fabric was embossed and then oven cured by heating for 2 hours at 260 F.

- The top coating (Example 3) was halogenated by treatment with a solution containing 6 percent sulfur chloride and 6 percent bromine in carbon tetrachloride followed by a treatment with a carbon tetrachloride solution containing 20 percent bromine. These treatments may be applied by brushing, dipping, flow application or other convenient means.

After the halogenation treatments, the coated fabric is passed through a chamber saturated with water vapor from low pressure steam and maintained at a temperature of about 140 F.

Commercial grade ammonia is fed into the chamber at the rate of two pounds per minute. The total neutralizing cycle was four minutes.

The upholstery material finished as described above exhibits exceptionally high-resistance to the abrasion, flex and scrub tests to which such materials are usually subjected. The new product'was particularly distinguished by its marked superiority in edge wear resistance, a property which is of great importance in upholstery constructions using a beading. The improved system also was found to afford excellent resistance to deterioration from exposure to sunlight. General durability on outdoor exposure was outstanding and a decided improvement in resistance to crocking as determined by rubbing with a wet cloth was observed. The finish exhibited desirable surface slip and excellent resistance to staining.

In the examples, a combined sulfur chloride and sulfur-chloride-bromine treatment is described.

' However, it is also possible to employ other halogenation-treatments. For example, it has been found that in some cases, notably where the top coat consists of chloroprene-acrylonitrlle interpolymer (Example 3) halogenation with bromine alone affords ever superior results.

The following composition was also found to be suitable as' an intermediate coating in the present invention and was prepared and applied as described above for Example 2.

As a top coat for the new finishing system, the following composition also provided excellent results particularly when used in conjunction with the intermediate coating of Example 4.

Example 5 Per cent by weight Neoprene (chloroprene-acrylonitrile interpolymer) 38.00 Anti-oxidant (MUF) .15 Circo oil 3.25 Zinc oxide 16.25 Kalite 15.18 Shellac 8.58 Magnesium oxide 1.50 Stearic acid .42

fAltax (Benzothiazyl disulfide) .21 Sulfur .21 Monastral blue pigment 3.25 Red iron oxide .28 Lead chromate yellow pigment 10.00 Channel black 2.72

This composition was prepared and applied over the intermediate composition of Example 4 in accordance with the procedure of Example 3. This coating was then halogenated by treatment with a 20 percent solution of bromine nd neutralized as in Example 3.

The use of shellac in the composition of Examples 4 and 5 provides a finish that is somewhat more rigid in the uncured state and sets quickly after leaving the calender rolls. t is not subject to cold flow and gives particularly good embossing definition. The shellac and "Kalite" modification also seems to further reduce chalking and crocking on extended expowas applied to then cal- Example 6 in Example 1' and The composition of cotton duck sateen as ender coated with and top-coated with the composition of Example 3 which was subsequently halogenated.

Example 7.--Intermediate coat Per cent by weight Butadiene-styrene interpolymer (Buna S) 35.70 Zinc oxide 15.30 "Kalite (stearic acid treated calcium carbonate) Z-mercaptotriazoline .50 Thionex (tetramethyl-thiuram mono- 25 sulfide) "Bara (dibutyl ammonium oleate) .38 Sulfur .70 Red lake (azo pigment dyestuffs) 6.11 100.00

The following composition may be substituted directly for Example 2 as an intermediate coating using the base coat of Example 1 and the topcoat of Example 3.

Example 8.'--Intermediate coat Per cent by weight Butadiene-acrylonitrile interpolymer (Per 'bunan") 34.80 'Ground leather 11.80 Zinc oxide 4.90 Red lake (azo pigment dyestuff) 5.90 Stearic acid .24 Crown clay 40.80 Plasticizer (processed mineral oil) .50 Accelerator (Zenite) .50

Thlonex (tetramethyl-thiuram-monosulfide) .06 Sulfur .50 100.00

. employed in conjunction with A system employing a base coat and an intermediate coating based on rubber may also be a topcoat such as Example 3 which is halogenated after its application as described above.

Example 9.-Base coat Percent by weight Rubber 10.0 Zinc oxide 10.0

. Rosin 9.0 Barytes 11.0

An anti-oxidant consisting of N, p-tolyl N, p-

a chloroprene-acryloresistant surface and for prene-acrylonitrile interpolymers are particu-- tolyl sulfonyl p-phenylene diarnine manufactured and sold by the Naugatuck Chemical Company as MUF was added in the proportion of 4 ounces for each 100 pounds of the above composition.

An intermediate coating consisting of the following composition may be calender coated over the base coat of Example 9 and finally the topcoat of Example 3 applied and halogenated as previously described.

Example 10.--Intermediate coat Percent by weight Rubber 34.43 Montan wax 6.27 Ground leather 15.65 Zinc oxide 15.65 Kalite" (stearic acid treated calcium carbonate) 16.70 Red lake (azo pigment dyestuff) 9.40 Accelerator (Zenite) .46 "Thlonex (tetramethyl-thiuram-monosulfide) .20 Barak (dibutylgammonium oleate) .20 Antioxidant (MUF) .27 Sulfur .17 100.00

90% zinc salt of 2-mercaptobenzothiazole and 10% hydrocarbon wax.

It is essential that the top coat be readily susceptible to halogenation to provide a hard, wear this purpose the chlorolarly outstanding. The sulfur modified neoprene which finds particular merit as an undercoat in the present system and other synthetic till - 7 zinc salt of 2-mercaptobenzothiazole and 10% hydrocarbon wax. s reduced much below 0.2

elastomers such as butadiene-styren'e interpolymers are difficult to halogenate and therefore are not suited for top coatings in the improved finishing' system; However, for undercoats, including base coats, they are satisfactory and contribute many important and necessary properties tothe overall superiority of the system. Thus the base coat and intermediate undercoats may consist of compositions containing acrylonitrile-butadiene interpolymers (Hycar, Perbunan) butadiene-styrene interpolymers (Buna S), rubber, sulfur modified neoprene or other such elastomers which are compatible with the special topcoat containing chloroprene-acrylonitrile interpolymer.

The thickness or wei ht of the several coatings in the present finishing system is important, particularly with respect to the top-coat. For most purposes, a coating weight '01 the chloroprene-acrylonitrile interpolymer composition (Example 3) of about 0.5 ounce per square 5 ounce per square yard 7 the abrasion resistance of the finish is unsatisfactory. In general, the coating weight of the top-coat nee not exceed about 1 The coating system is not limited to any particular type of fabric but may be employed with various supporting base fabrics, including cotton fabric (duck-sateen, etc), nylon, Fibre A, paper, rayon, etc.

appreciable degree with e halogen The c loroprene-acrylonitrile interpolymer top-coats when us treated afford surface which The primary utility of the new finishing system involves th products where are most desirable.

dge wear is esis likewise applicable to the coating of ible and semi-rigid,

material, counters, caps and uppers and as material for bookbinding.

The present invention is characterized by advantages. A remarkably in upholstery e new coatconventional finis retained for more extended periods. The

system proso that only a about 18% of acrylonitrile.

3. Process of claim 2 in which the size coating and intermediate coating comprise a sulfur modcoat comprises a in which the halogenation comprises treatment with bromine.

cluding at least one undercoat and a topcoat, the said underc'oat comprising an elastomer selected from the group consisting of rubber, chloper square yard and the topcoat in amount of about 0.5 ounce per square yard.

8. An improved upholstery fabric carrying a plurality of coatings consisting of a size coat, an intermediate coat and a halogenated topcoat, the said size coat and intermediate coats comprising an elastomer selected from the group consisting of rubber, chloroprene, and interpolymers of acrylonitrile-butadiene and butadienestyrene and the said topcoat comprising a chloroprene-acrylonitrile interpolymer surface halogenated with material selected from the group consisting of chlorine and bromine, said interpolymer containing about 18% of acrylonitrile.

9. Product of claim 8 in which the size coat and intermediate coat comprise a sulfur modified chloroprene and the topcoat comprises a halogenated chloroprene-acrylonitrile interpolymer.

Number 10 10. Product of claim 8 in which the size coat is present in an amount of about two ounces per ,square yard, the intermediate coat in amount of about 9.5 ounces per square yard and the topcoat in an amount of about 0.5 ounce per square yard.

11. A fabric carrying a plurality of coatings including at least one undercoat and a topcoat, the said undercoat comprising an elastomer selected from the group consisting of rubber, chloroprene and interpolymers of acrylonitrilebutacliene and butadiene-styrene and the said topcoat comprising shellac and a chloropreneacrylonitrile interpolymer surface halogenated with material selected from the group consisting of chlorine and bromine, said intrpolymer containing about 18% of acrylonitrile.

DAVID J. SULLIVAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Collins et al July 24, 1934 Hobgood et al. Jan. '7, 1941 Sarbach Apr. '7, 1942 Langkammerer Nov. 17, 1942 Carothers et a1. Feb. 4, 1936 Sarbach Feb. 19, 1946 

